Insecticidal compositions and methods employing naphthyl fluoroacetamides



United States Patent US. Cl. 424--324 Claims ABSTRACT OF THE DISCLOSUREThis invention relates to certain novel N-substituted fiuoroacetamidesvaluable as insecticides and suitable in particular for use asplant-protecting agents, and relates to certain new processes forpreparing them.

This application is a continuation application of Ser. No. 422,523,filed Dec. 31, 1964, and now abandoned.

The novel compounds in the present invention are characterized by thestructural Formula I.

wherein Ar is selected from the group consisting of a phenyl radical, achlorophenyl radical, a trichlorophenyl radical, a fluorophenyl radical,a nitrophenyl radical, a napthyl radical; a thiazolyl radical, adimethylthiazolyl radical, a nitrothiazolyl radical and athiocyanatothiazolyl radical, and R is selected from the groupconsisting of an alkyl radical containing at most 4 carbon atoms, ahydroxyalkyl radical containing from 2 to 4 carbon atoms, a benzylradical and a naphthylmethyl radical.

These compounds have the outstanding characteristic of being lesspoisonous to warm blooded animals but not less toxic to insects such asmite, scale and their preemergence (egg) in comparison ofN-unsubstituted fluoroacetamides such as the compounds represented byFormula I wherein R is hydrogen. Our improved compounds may be preparedaccording to the following Equations A and B and B ArN--C O C HaFwherein R is lower alkyl radical. 7

These reactions are well-known and proceeding smoothly, but theseprocesses have a decisive fault that fluoroacetylchloride as startingmaterial is volatile and extremely strongly poisonous to human beings aswell as warm blooded animals.

The processes proposed in this invention comprise a novel reaction ofamine hydrochlorides with fiuoroor chloroacetic acid in the presence ofchlorides of phosphorus and do not comprise the reaction offluoroacetylchloride, and they are shown in Equations C and D and Dchloride of phosphorous Arl}IH-HC1 XCHzC O OH wherein X is chlorine orbromine atom.

In the process C, the reaction is proceeding smoothly in an inactive andanhydrous solvent in the presence of chloride of phosphorus such as PO1PO1 and POCl at the temperature of 20-140 C. especially C.

In the process consisting of step D and D the first step D is proceedingin the same manner as the process C, except to apply chloroacetic acidinstead of fiuoroacetic acid as a reactant; the second step D is the newprocess in the application for N-substituted fluoroacylamide and itproceeds in a glycol such as ethyleneglycol, diethyleneglycol, lowerpolymer of ethyleneglycol or their lower alkyl ether e.g.methylcellosolve and ethylcellosolve at the temperature of 100300 C.especially -160 C.

The reaction of fluorination of chloroacylamide with potassium fluoridehas not been known and is scarcely carried out because of low yield dueto hydrolysis of the chloroacyl group. But, in our investigation, theundesirable hydrolysis was prevented and the yield of the aimed compoundwas increased sufliciently to be suitable as an industrial method by theintroduction of a group in the N-position of chloroacetylamide.

The following examples will illustrate certain of the many specificembodiments of the invention.

EXAMPLE 'I N-methyl-N-(l-naphthyl) -fluoroacetamide (Compound I) for aperiod of /21 hour. Then, the mixture was heated V at 135l40 C. for 1-2hours. Inthe mixture, crystals of.

amine hydrochloride separated out and red or reddish brown oxides ofphosphorus appeared at the bottom of reactor. The liquid layer waspoured in a distillator and the solvent was removed. The raw crystalswere obtained as the residue, and washed by water and dried. Obtainedwere 18.4 g. of colorless plates, N-methyl-N-(l-naphthyl)-fluoroacetamide, M.P. 87-88 C.

Analysis.Calculated for C H FNO: N, 6.45%. Found: N, 6.37%.

(B) A solution of 5.4 g. of P01 in anhydrous xylene was added dropwiseto a suspension of 47.2 g. of N-methyla-naphthylamine hydrochloride and18.8 g. of bromoacetic acid in 240 ml. of anhydrous xylene at atemperature of 90100 C. for a period of /2-1 hour under agitation. Then,the mixture was heated at 135-140 C. for l-2 hours. The liquid layer ofthe mixture was poured and distilled to remove the solvent, 30.5 g. ofcolorless plates, M.P. 6667.5 C., ofN-methylN-(1-naphthyl)-bromoacetamide was obtained from the residueafter washing with water and drying. 4

27.8 g. of N-methyl-N-(l-naphthyl)-bromoacetamide and 11.6 g. ofanhydrous potassium fluoride were added to 48 ml. of ethyleneglycol, andthe mixture wa heated at 130-135 C. for 1.5 hours under agitation. Then,the mixture was cooled to room temperature and poured in 300 ml. of coldwater.

Raw crystals were separated. The crystals were washed satisfactorilywith water and dried, and recrystallized in a mixed solvent of n-hexaneand n-butanol. 16.6 g. of colorless plates, M.P. 87-88 C., ofN-methyl-N-(lnaphthyl) -fluoroacetamide were obtained.

EXAMPLE II N-methyl-Z 4 5-trichloro-fluoroacetanilide (Compound 11) Asolution of 10.1 g. of POCI, in anhydrous xylene was added dropwise to amixture of 26.4 g. of 2-4-5-trichloroaniline hydrochloride and 12.6g.-of chloroacetic acid in 160 ml. of anhydrous xylene at thetemperature of 90-100 C. for a period of /z-1 hour under agitation.Then, the

mixture was heated at l35-140 C. for 1-2 hours. The

liquid layer of the mixture was poured and distilled to remove thesolvent, and 31.0 g. of colorless needles, M.P. 83-84" C., ofN-methyl-2-4-5-trichloro-chloroacetanilide was obtained from the residueafter washing by water and drying.

28.7 g. of N-methyl-2-4-S-trichloro-chloroacetanilide separated. Thecrystals were washed thoroughly with water and dried, and recrystallizedin a mixed solvent of nhexaneand n-butanol- 21.8 g. ofewhite platecrystals were obtained. M.P. 117-l80 C.

Analysis.Calculate.d for. C H Cl FNO2 N, 5.71%. Found: N, 5.31%.

EXAMPLE III 2-(N-methylfiuoroacetamido)-4,5 dimethylthiazole (CompoundIII) A solution of 7.6 g. of PCL in anhydrous xylene was "added dropwiseto amixture of 17.8 g. of Z-methylamino- 4,5-dimethylthiazolehydrochloride and 8.6 g. of fluoroacetic acid in 130 ml. of anhydroustoluene at the temperature of l00 C. for a period of /21 hour underagitation. Then, the mixture was heated at 135140 C.

forv l-2 hours. The liquid layer of the reaction mixture was poured anddistilled to remove the solvent, and 17.6 g; ot colorless needles, M.P.-116 C., were obtained from the residue after washing with water anddrying.

Analysis-Calculated for C H FN OS: N, 13.87%. Found: N, 14.46%.

EXAMPLE 1v N-3-dimethyl--fiuoroacetanilide (Compound IV) A solution of 5g. of PCI in anhydrous xylene was added dropwise to mixture of 15.8 g.of N-3-dimethyl aniline hydrochloride and 8.6g. of fluoroacetic acid in150 ml. of anhydrous toluene at the temperature of 90100 C. for a periodof /21 hour under agitation. Then, the mixture was heated at 135-l40 C.for 1 2 hours. The liquid layer of the mixture was poured and distilledto remove the solvent, and 15.3 g. of colorless needles, M.P. 86-87 C.,were obtained from the residue after washing with water and drying.

Analysis.-Calculated for C H FNO: N, 7.73%. Found: N, 8.09%.

EXAMPLE V 2- (N-methylfluoroacetamido)-thiazole (Compound V) '19 g. of2-(N-methylchloroacetamido)-thiazole and 11 g. of potassiumfluorideanhydridewereadded to 50 ml. of ethyleneglycol, and the mixture washeated at C. for 2 hours. Then, the mixture was cooled to roomtemperature and poured into 300 m1. of cold water. The raw crystals wereseparated. The crystals were washed by water and dried, andrecrystallized in a mixed solvent of n-hexaneandn-butanol. 13.2 gaof2-(N=methylflnoroacetamido)- thiazole were obtained. M.P. 154-155 C.

- .Analysis.--Calculated for C H FN OS: N, 16.10%,

Found:N;'l5.80'%;"

EXAMPLE v1 37.1 g. of N-ethyl-(l-naphthyl)-chloroacetamide and 17.4 g.of anhydrous potassium fluoride were added to 100 ml. of ethyleneglycol,and the mixture was heated -at-' l30- 135 C. for 2 hours underagitation. Then, the mixture was cooled to room temperature and pouredinto 500 ml. of cold water. The precipitates were gathered by filtrationand washed with water and dried, and recrystallized in a mixed solventof n-hexane and n-butanol. 27.4 g.

of colorless plates were obtained. M.P. 89-90 C.

Analysis.Calculated. ,for C H FNO: N, 6.06%.

'FoundzN, 6.14%.

In addition to above mentioned compounds described in the precedingexamples, some of typical compounds of the present invention are listedin Table 1.

a part of compounds of the present invention, so that the objectives ofthe present invention are not limited only TABLE 6 6 in those compoundslisted in Table I.

Ar-r l-oo 031mv R Analysis forN (percent) N0. of [M.P.](B.P.) m compd A:R C./mm. Hg Formula Found Calcd.

oH3 [88-891 CsHioFNO 8.17 8.65

VIII [81-82] CmHmFNO 5. 00 4. 78

XI Q 0H.-. [70-71] (97-98) 0.25 COHQFQNO 7.38 7. 56 x Q -oH,oH=oH143-144 0.1 o HumNo, 6.65 6.51

x1 C1 -CH;CH:OH [s4-s51 (134-135) 0.1 CIOHHCIFNO: 5.95 6.05

XII --CH:| [115-116] CDHBF IOB 12.85 13. 22

NO I

XIII 1 C1. C2H5 [80-81] CmHoClsF 5.22 4. 92

'XIV 01110116011 (189-190) 0.2 CuHuFNOfl 5.82 5.66

XV .1 CH3 Viscous liquid. C HNFNOz 5. 52 5. 36

Jan-0112011 XVI [89-901 CnHmFN 5.07 4.78

XVII

CH3 [105-1061 CnHnFNO 6.65 6. 45

grvrn I I V on; Viscous liquid. CuHmFNOg 5.14 5.36

xixi 3 4H, 1107-1081 Cin ioF 4.95 4.78

'xx -N -CH3 1144-1451 C HgFN OzS 18.98 19.18

NOz- J S XXL. N -CH; [136-137] C7HaFN3OS1 18.06 is. 19

7 EXAMPLE VII Emulsive agent Parts by weight Compound III 20 Dimethylformamide 35 Xylene 38 Nonionic surfactant 7 These were mixed anddissolved. In practical use, this solution was diluted in LOGO-2,000times the amount of water to produce the suspension, which was appliedas a spray for use in accordance with the invention.

EXAMPLE VIII Emulsive agent Parts by Weight 25 Compound I Cyclohexanone3O Toluene 35 Nonionic surfactant 5 Alkylbenzenesulphonate 5 These weremixed and dissolved altogether. For practical use, the emulsive solutionwas diluted in 1,000- 2,000 times the amount of water and sprayed overthe vegetation.

EXAMPLE 1X Hydration agent Parts Compound II 25 Higher alcohol sulphate5 Diatomaceous earth 70 These were mixed altogether and then crushed infine powders. In practical use, the mixture was diluted with water toproduce the suspension; and was sprayed.

EXAMPLE X Hydration agent Parts Compound XIII 30Alkylarylsorbitanlaurate 8 Hifiow-supercell 62 These were mixed andcrushed in fine powders to produce the hydration agent.

In practical use, the mixture was diluted with water in an appropriateratio, and this suspension was sprayed.

EXAMPLE XI Powder agent Parts Compound 11 5 Talc 94.9Alkylallylpolyoxyethylene 0.1

These were mixed and crushed to a fine powder. The powder agent wassprayed.

EXAMPLE XII Hydration agent Parts Compound I 204-chlorophenyl-4-chlorobenzene sulfonate 25 Diatomaceous earth 45Polyoxyethylenealkylphenylether These components were mixed and crushedinto a fine powder to prepare the hydration agent. For practical use,the hydration agent was diluted by water in an appropriate 'ratio; andthe suspension was sprayed.

In Examples VII-XII, anionic surfactants, for examplealkbenzensulphonate or higher alcohol sulphonate; and nonionicsurfactants, for example alkylarylpolyoxyethylene oralkylarylsorbitanelaurate, may be used as emulsifying, wetting ordispersing agents. Talc, kaolin apd diatomaceous earth can be used ascarrier. Xylene and toluene can be used as the solvent.

Insecticidal and miticidal effect of the novel compounds of theinvention are shown by the following tests.

TEST I Insecticidal effect to housefly (Musca ddmestica)-- 5 (topicalapplication method) Female adults of housefly (Musca domestica) in aperiod of three days after emergence, which are resistant againstdichlorodiphenyl trichloroethane (DDT) and were provided by InfectionsDisease Research Institute, were tested by topical application method;the acetone solutions of the various compounds were applied to thefemale adults of housefly and mortalities were investigated in thecourse of 24 hours. The results are shown in Table II.

TABLE II.MORTALITY OF TOPICAL APPLICATION FOR ADULT FLIES.

Mortality Mortality No. of compound (percent) N o. of compound (percent)N 0TE.DOS9 of application, 107 compound/fly.

TEST II Insecticidal effect to weevil (Curculionidae species, Bruchuspisorum)-(dipping method) Adults of weevil in a period of 24 hours orless after emergence were dipped in the acetone solutions of varioustested compounds in a period of 3 seconds, and the mortalities in thecourse of 48 hours were investigated. The result is shown in Table III.

Insecticidal efiect to peach red aphid (Cinara species)-(pot test) Thedilute solution of the tested compounds were sprayed over peach redaphids which were parasitic on radish (Raphances sativus) grown in 12cm. diameter of pots in a green house, and the mortalities wereinvestigated in the course of 24 hours.

TABLE IV.MORTALITY (PERCENT) FOR PEACH RED APHID IN POT TEST Content ofcompd. in

Content of compd. in

suspn. suspn. No. or No. of

compd. 0. 025% 0.005% compd. O. 025% 0.005% 100 66 TEST IV Insecticidaland ovicidal effects to citrus red mite (Panonychus 'citri) glassplate'method) Leaves of Sommer orange (Citrus auran'tium natsudaidaiMakino et -Nemoto) infested with citrus red mites w e e edin nsx h ir nhe sleave w r p into glass plates with lids one by one. Then, on theleaves, the

75 water suspensions of hydration agents including a difier- 9 1O enttested compound are sprayed respectively. Insecticidal mortality wasinvestigated in the course of one month and ovicidal data were shown inTable V. after sprayed.

TABLE V.-INSEOTIOIDAL AND OVICIDAL EFFECTS TO CITRUS RED MITE Mortality(percent) Adult Egg Content of compd. in suspn. a Content of compd. insuspn. N 0. i compd. 0. 05% 0. 025% 0. 0125% 0. 003% 0. 05% 0. 025% 0.0125% 0. 003% TEST V TABLE vIL-INsECTIoIgJ L EFFECT T0 ARROWHEADInsecticidal effect to two-spotted spider mite (Tetranychustebarz'us)(pot test) o y, (pe f Mortality (p ce No. Compd. Larva AdultCompd. Larva Adult About "female adults of two spott ed spider mite(Tetranychus tebarius) are made tomigrate upon main leaves of kidneybeans which were sowed and sprouted on 6 cm. diameter pots and left for7 to 10 days. After one day the water suspensions of hydration agentscon taining a 0.05% of different tested compounds were sprayed on theleaves respectively.-3 days after spraying, the mortality of adults wasinvestigated, and all adults were removed. The eggs on the leaves wereobserved for TEST VII a period of 7 days, to find out how many of themcould Insecticidal effect to white peach scale not incubate.

(Pseudococcus comstockz) Then, the larvae were observed for 5 days tosee I, V V V, 7 H l Whether they could grow to adults. v A watersuspension containing 0.05% or 0.025% of Insecticidal and ovicidal dataare shown in Table VI. tested compound was sprayed on pumpkin (Curcurbiaspecies) infested with female adults of white peach scale TABLEVL'JNSECTICIDAL OVICIDAL EFFECTS To of pri-oviposition. Then, themortality-was investigated in TWO-SPOTTED SPIDER MITE a Pel'lOdOf threedays after sprayed.

yr li t M r in t r No. of m TABLE VIII.INSECTIOIDAL EFFECT TO'WHI'IEPEACH compd. Adult Egg Adult Egg SCALE 100 100 100 100 No. of Mortality(percent) N o. of Mortality (percent) 100 100 100 100 :eompd. ricom a .7.v 100 100 100 0. 05% 0. 025% 0. 05% 0. 025% 100 100 100 100 100 95 100100 77 78 100 100 87 51 s4 79 100 100 100 89 XII 100 75 50-100 100 98100 60 100 100 100 100 100 TEST VIII TEST VI Acute oral toxicity formouse Value of LD for mouse relating to tested com-pound Insectlcldalefiect t0 0W1}ead Scale 60 was measured by the usual method and theresult is shown (Unaspis Yanonenszs) i T bl 1 A. Insecticidal effect tolarva.Leaves mandarin orange TABLE ORAL TOXICITY FOR MICE (Citrus unshiuMarc.) infested with female Znd-instar Ar NC--CH F larvae of arrowheadscale were collected in an orchard. R 0 These leaves were put into glassplates with lids one by No. of LDw (mg/kg.) one. Then, on the leaves,the water suspensions of hyc0mPd- AI R 05 mouse) dration agentsincluding a 0.05% of diflerent tested compounds were sprayedrespectively. In the course of 17 IX 50 days after sprayed, themortality was investigated on an assumption that the ones not grown from2nd-instar larvae X CHTOH to immature adults were taken as dead.

B. Insecticidal effect to adult-Leaves of mardarin orange infested withfemale adults of arrowhead scale XI Cl- 32 were collected and treated inaccordance with A. The 7 x11 NOa-Q- CH3 as om Iv OH; as

I 11 Cl -CH3 187 l or I Cl- -02H5 167 I or I -H3 s72 XIV Q- OH2-CH;-OH14s XV Q- (lJH-CHz-0H 108 g 2 on,

xvrr. CH: 63

- -o11-orn-0H o XIX.--.- -CH;@ 241 We claim:

1. Insecticidal composition, comprising :a carrier adapted forapplication to areas of insect infestation, and an insecticidallyeffective amount of a compound of the formula:

wherein Ar is naphthyl and wherein R is selected from the groupconsisting of alkyl of up to 4 carbon atoms, hydroxyalkyl of 2-4 carbonatoms, benzyl and naphthylmethyl.

2. Composition according to claim 1 wherein said compound isN-methyl-N-(l-naphthyl)-fiuoroacetamide.

3. Insecticidal composition according to claim 1 wherein R isnaphthylmethyl.

4. Method of killing insects, which comprises contacting the insects tobe killed with an effective amount of a compound of the formula:

wherein Ar is naphthyl and wherein R is selected from the groupconsisting of alkyl of up to 4 carbon atoms, hydroxyalkyl of 2-4 carbonatoms, benzyl and naphthylmethyl.

5. Method according to claim 4 wherein R is naphthylmethyl.

References Cited UNITED STATES PATENTS 2,409,315 10/ 1946 Rigby et al260-562 2,863,752 12/1958 Hamm et a1. 260-562 2,409,315 10/ 1946 Rigby260--561 3,255,247 6/1966 Olin 260-562 OTHER REFERENCES Bergmann et al.:Chem. Abstracts, vol. 51, col. 17073f (1957 Hickenbottorn: Reactions ofOrganic Compounds (London, 1948), pp. 227-230 and 294-298.

Lovelace et al.: Aliphatic Fluorine Compounds (New York, 1958), pp. 3,220 and 261-262.

Chem. Abstracts, vol. 51, p. 1707315 (1957).

ALBERT T. MEYERS, Primary Examiner.

S. FRIEDMAN, Assistant Examiner.

US. Cl. X.R.

